Catalyst components for the polymerization of olefins

ABSTRACT

Catalyst component for the polymerization of olefins comprising Mg, Ti and an electron donor of formula (I) 
                         
In which X and Y are selected from, R 1 , and —OR 1  and —NR 2 , B is oxygen or sulphur S is sulphur, R 1  is selected from C 1 -C 15  hydrocarbon groups, optionally contain a heteroatom selected from halogen, P, S, N, O and Si, which can be fused together to form one or more cycles, R is hydrogen or R 1  and A is a bivalent bridging group with chain length between the two bridging bonds being 1-10 atoms.

This application is a Divisional Application that claims benefit to U.S.Non-Provisional application Ser. No. 14/891,949, filed Nov. 17, 2015,that is the U.S. National Phase of PCT International ApplicationPCT/EP2014/059938, filed May 15, 2014, claiming priority of EuropeanPatent Application No. 13168358.3, filed May 17, 2013, the contents ofwhich are incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure relates to the field of chemistry. In particularit relates to catalyst components for the polymerization of olefins, inparticular propylene, comprising a Mg dihalide based support on whichare supported Ti atoms and an electron donor selected from a specificclass of mercaptoalcohol derivatives. The present disclosure furtherrelates to the catalysts obtained from said components and to their usein processes for the polymerization of olefins in particular propylene.

BACKGROUND OF THE INVENTION

Catalyst components for the stereospecific polymerization of olefins arewidely known in the art. Concerning the polymerization of propylene, themost spread out catalyst family belongs to the Ziegler-Natta categoryand in general terms it comprises a solid catalyst component,constituted by a magnesium dihalide on which are supported a titaniumcompound and an internal electron donor compound, used in combinationwith an Al-alkyl compound. Conventionally however, when a highercrystallinity of the polymer is required, also an external donor (forexample an alkoxysilane) is needed in order to obtain higherisotacticity. One of the preferred classes of internal donors isconstituted by the esters of phthalic acid, diisobutylphthalate beingthe most used. The phthalates are used as internal donors in combinationwith alkylalkoxysilanes as external donor. This catalyst system givesgood performances in terms of activity, isotacticity and xyleneinsolubility.

One of the problems associated with the use of this catalyst system isthat the phthalates have recently raised concerns due to the medicalissues associated with their use and some compounds within this classhave been classified as source of heavy health problems.

Consequently, research activities have been devoted to discoveralternative classes of internal donors for use in the preparation ofcatalyst components for propylene polymerization.

Internal donors are described in U.S. Pat. No. 7,388,061 andWO2010/078494 which both relate to esters of aliphatic or aromaticdiols. Both the references do not describe possible alternatives tothese structures. Moreover, in view of the fact that their basicstructure is that of a diol, it is difficult to produce multifunctionderivatives with different functional groups (ester/ether,ester/carbamate etc) because the two oxygens of the diol basic structurehave identical reactivity.

Surprisingly, the applicant has found that a particular class of donorsbased on mercapto derivatives is suited to generate a wide arrange ofmolecules with equal or different functional groups which when used asinternal donors generate catalysts showing an excellent balance ofactivity and stereospecificity.

SUMMARY OF THE INVENTION

Accordingly, it is provided a catalyst component for the polymerizationof olefins comprising Mg, Ti and an electron donor compound of formula(I)

In which X and Y are selected from, R¹, and —OR¹ and —NR₂, B is oxygenor sulphur S is sulphur, R¹ is selected from C₁-C₁₅ hydrocarbon groups,optionally contain a heteroatom selected from halogen, P, S, N, O andSi, which can be fused together to form one or more cycles, R ishydrogen or R¹ and A is a bivalent bridging group with chain lengthbetween the two bridging bonds being 1-10 atoms.

DETAILED DESCRIPTION OF THE INVENTION

In case of cyclic structures acting as bridging groups the term “chainlength” is referred to the shortest sequence of atoms bridging the twosulphur or oxygen/sulfur atoms of formula (I). In some embodiments, thebridging group has formula —(ZR² _(m))_(n)— in which, independently, Zis selected from C, Si, Ge, O, N, S or P, the R² groups, equal to ordifferent from each other, are hydrogen or a C₁-C₂₀ hydrocarbonradicals, optionally containing a heteroatom selected from halogen, P,S, N, O and Si, which can be fused together to form one or more cycles,m is a number satisfying the valences of Z and n is an integer rangingfrom 1 to 10. In certain embodiments, for the bridging group having theformula —(ZR² _(m))_(n)— the atoms O, S, and N are not directly linkedto the S or O of formula (I), i.e. O, S, and N are not the terminalatoms of the bridging group. In some embodiments, Z is selected from Cand Si. In further embodiments, Z is carbon.

In a particular embodiment, the said bivalent bridging group is selectedfrom the group consisting of aliphatic, alicyclic and aromatic bivalentradicals, optionally substituted with C₁-C₁₅ hydrocarbon groups and/orwith heteroatoms selected from halogen, P, S, N, O and Si, and having abridging chain length ranging from 1 to 6 atoms including 1 to 4 atoms.

In some embodiments, the bridging group is an aliphatic or alicyclicbridging group having a bridging chain length of 2-3 carbon atoms. Amongthis class, bridging groups may include those of formula —(CR³_(p))_(s)— in which R³ is independently hydrogen or a C₁-C₂₀ hydrocarbonradicals, optionally substituted with heteroatoms selected from halogen,P, S, N, O and Si, which can be fused together to form one or morecycles, p is a number satisfying the available valence of carbon and sis a number from 1 to 6 including from 1 to 4. Examples of bridginggroups are methyliden, ethane-1,2-diyl, butane-2,3-diyl,pentane-2,4-diyl, 2,2-diisobutylpropane-1,3-diyl, cyclohexane-1,2-diyl,cyclopentane-1,2-diyl.

A subclass for use in the present technology is that of formula (II)below:

in which B is sulfur or oxygen in which R⁴-R⁷ groups, equal to ordifferent from each other, are hydrogen or C₁-C₁₅ hydrocarbon groups,optionally containing an heteroatom selected from halogen, P, S, N andSi, and R⁸ equal to or different from each other, are selected fromC₁-C₁₅ hydrocarbon groups which can be optionally linked to form a cycleand n is an integer from 0 to 5.

B in formula (II) may be sulfur, R⁴ and R⁷ are selected from C₁-C₁₀alkyl groups including C₁-C₅ alkyl groups such as methyl, and R⁵ and R⁶are selected from hydrogen or C₁-C₁₀ alkyl groups. R⁸ groups areindependently selected from C₁-C₁₀ alkyl groups such as methyl, ethyl,n-propyl and n-butyl. The index n can vary from 0 to 5 inclusive,including from 1 to 3. When n is 1, the substituent R⁸ may reside inposition 4 of the benzoate ring.

Another bridging group for use in the present technology is the onebased on cyclic aromatic groups which through the carbon ring atoms canlink the two sulphur or sulphur/oxygens atoms of formula (I). Amongthem, the phenyl groups, optionally substituted with halogens or C₁-C₂₀alkyl radicals, bridging the oxygen atoms in position 1,2 or 1,3 or 1,4and the naphthalene groups, optionally substituted bridging the oxygengroups in position 1,2 or 2,3 or 1,8 may be used.

Among them, the structure of formula (III) below:

in which X, Y and B have the same meaning specified in claim 1, andR⁹-R¹² independently, are selected from hydrogen, halogens or C₁-C₁₅hydrocarbon groups optionally substituted with heteroatoms selected fromhalogen, P, S, N, O and Si may be used in accordance with the presenttechnology.

Structures of formula (III) are those in which the groups R⁹, R¹¹ and/orR¹² are C₁-C₅ alkyl groups including those in which R⁹ and/or R¹² are aprimary alkyl group such as methyl, and R¹¹ is a tertiary alkyl groupsuch as tert-butyl.

Specific examples are 1,2-phenylene, 3-methyl-1,2-phenylene,4-chloro-1,2-phenylene, 4-(tert-butyl)-1,2-phenylene,3,6-dimethyl-1,2-phenylene, 3,5-dimethyl-1,2-phenylene,5-(tert-butyl)-3-methyl-1,2-phenylene, 3,5-diisopropyl-1,2-phenylene,naphthalene-1,8-diyl, naphthalene-1,2-diyl, naphthalene-2,3-diyl groups.

In some embodiments, B in formulas (I) and (III) is oxygen. Moreover, R¹groups are selected from C₁-C₁₀ alkyl groups and C₆-C₁₅ aryl oralkylaryl groups including linear C₁-C₅ alkyl groups such as methyl,ethyl and propyl while aryl or alkylaryl groups are phenyl groupsincluding those substituted with halogen and/or C₁-C₅ alkyl groups.

Possibilities of combinations between X and Y groups of formulae (I) and(III) are those in which B is O, X is R¹ and Y is selected from thegroup consisting of R¹, —OR¹ and —NR₂ in which R¹ and R have themeanings explained above. In some embodiments both X and Y are selectedfrom R¹ and in particular from C₆-C₁₅ aryl or alkylaryl groups. Anothercombination is that in which B is O, X is —OR¹ and Y is selected from—NR₂ and —OR¹. According to a further embodiment, B is O, X is a —R¹group selected from C₆-C₁₅ aryl or alkylaryl groups and Y is —OR¹ inwhich R¹ is selected from C₁-C₁₀ alkyl group.

In the —NR₂ groups the R radicals are selected from C₁-C₁₀ alkyl groupsincluding linear C₁-C₅ alkyl groups such as methyl, ethyl and propyl.

The final amount of electron donor compound in the solid catalystcomponent may range from 1 to 25% by weight preferably in the range from3 to 20% by weight.

Non limiting examples of structures of formulas (I) and (II) are thefollowing: 2-(benzoylthio)-4-(tert-butyl)-3,6-dimethylphenyl benzoate,2-(benzoylthio)-4-(tert-butyl)-6-methylphenyl benzoate,4-(tert-butyl)-2-((3-chlorobenzoyl)thio)-3,6-dimethylphenyl3-chlorobenzoate,4-(tert-butyl)-2-((3-chlorobenzoyl)thio)-6-methylphenyl3-chlorobenzoate,4-(tert-butyl)-2-((diethylcarbamoyl)thio)-3,6-dimethylphenyl benzoate,4-(tert-butyl)-2-((diethylcarbamoyl)thio)-6-methylphenyl benzoate,4-(tert-butyl)-2-((dimethylcarbamoyl)thio)-3,6-dimethylphenyl benzoate,4-(tert-butyl)-2-((dimethylcarbamoyl)thio)-6-methylphenyl benzoate,4-(tert-butyl)-2-methyl-6-((4-propylbenzoyl)thio)phenyl4-propylbenzoate,4-(tert-butyl)-3,6-dimethyl-2-((4-propylbenzoyl)thio)phenyl4-propylbenzoate,S-(3-(tert-butyl)-6-((diethylcarbamoyl)oxy)-2,5-dimethylphenyl)benzothioate,S-(3-(tert-butyl)-6-((dimethylcarbamoyl)oxy)-2,5-dimethylphenyl)benzothioate,S-(5-(tert-butyl)-2-((diethylcarbamoyl)oxy)-3-methylphenyl)benzothioate,S-(5-(tert-butyl)-2-((dimethylcarbamoyl)oxy)-3-methylphenyl)benzothioate,4-(tert-butyl)-2-((diethylcarbamoyl)thio)-3,6-dimethylphenyldiethylcarbamate, 4-(tert-butyl)-2-((diethylcarbamoyl)thio)-6-methylphenyl diethylcarbamate,4-(tert-butyl)-2-((dimethylcarbamoyl)thio)-3,6-dimethylphenyldimethylcarbamate,4-(tert-butyl)-2-((dimethylcarbamoyl)thio)-6-methylphenyldimethylcarbamate,4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3,6-dimethylphenyl ethylcarbonate, 4-(tert-butyl)-2-((ethoxycarbonyl)thio)-6-methylphenyl ethylcarbonate, S,S′-(4-(tert-butyl)-3,6-dimethyl-1,2-phenylene)dibenzothioate, S,S′-(4-(tert-butyl)-3-methyl-1,2-phenylene)dibenzothioate,S-(3-(tert-butyl)-6-((diethylcarbamoyl)thio)-2,5-dimethylphenyl)benzothioate,S-(3-(tert-butyl)-6-((diethylcarbamoyl)thio)-2-methylphenyl)benzothioate,S-(3-(tert-butyl)-6-((ethoxycarbonyl)thio)-2,5-dimethylphenyl)benzothioate, S-(3-(tert-butyl)-6-((ethoxycarbonyl)thio)-2-methylphenyl)benzothioate,S-(4-(tert-butyl)-2-((diethylcarbamoyl)thio)-3,6-dimethylphenyl)benzothioate,S-(4-(tert-butyl)-2-((diethylcarbamoyl)thio)-3-methylphenyl)benzothioate,S-(4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3,6-dimethylphenyl)benzothioate, S-(4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3-methylphenyl)benzothioate, S,S′-(4-(tert-butyl)-3,6-dimethyl-1,2-phenylene)O,O′-diethyl dicarbonothioate,S,S′-(4-(tert-butyl)-3,6-dimethyl-1,2-phenylene)bis(diethylcarbamothioate), S,S′-(4-(tert-butyl)-3-methyl-1,2-phenylene)O,O′-diethyl dicarbonothioate,S,S′-(4-(tert-butyl)-3-methyl-1,2-phenylene) bis(diethylcarbamothioate),S-(3-(tert-butyl)-6-((ethoxycarbonyl)thio)-2,5-dimethylphenyl)diethylcarbamothioate,S-(3-(tert-butyl)-6-((ethoxycarbonyl)thio)-2-methylphenyl)diethylcarbamothioate,S-(4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3,6-dimethylphenyl)diethylcarbamothioate,S-(4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3-methylphenyl)diethylcarbamothioate, S,S′-(4-(tert-butyl)-3,6-dimethyl-1,2-phenylene)bis(4-propylbenzothioate),S,S′-(4-(tert-butyl)-3,6-dimethyl-1,2-phenylene)bis(3-chlorobenzothioate), 4-((diethylcarbamoyl)thio)pentan-2-ylbenzoate, 4-((ethoxycarbonyl)thio)pentan-2-yl benzoate,4-(benzoylthio)pentan-2-yl benzoate, S,S′-pentane-2,4-diyldibenzothioate, S-(4-((diethylcarbamoyl)oxy)pentan-2-yl) benzothioate,S-(4-((diethylcarbamoyl)thio)pentan-2-yl) benzothioate,S-(4-((ethoxycarbonyl)oxy)pentan-2-yl) benzothioate,S-(4-((ethoxycarbonyl)thio)pentan-2-yl) benzothioate,4-((diethylcarbamoyl)thio)pentan-2-yl diethylcarbamate,4-((ethoxycarbonyl)thio)pentan-2-yl diethylcarbamate,4-((ethoxycarbonyl)thio)pentan-2-yl ethyl carbonate, O,O′-diethylS,S′-pentane-2,4-diyl dicarbonothioate, S,S′-pentane-2,4-diylbis(diethylcarbamothioate), S-(4-((ethoxycarbonyl)oxy)pentan-2-yl)diethylcarbamothioate, S-(4-((ethoxycarbonyl)thio)pentan-2-yl)diethylcarbamothioate, 4-((3-chlorobenzoyl)thio)pentan-2-yl3-chlorobenzoate, 4-((diethylcarbamoyl)thio)pentan-2-yl3-chlorobenzoate, 4-((ethoxycarbonyl)thio)pentan-2-yl 3-chlorobenzoate,S,S′-pentane-2,4-diyl bis(3-chlorobenzothioate),S-(4-((diethylcarbamoyl)oxy)pentan-2-yl) 3-chlorobenzothioate,S-(4-((diethylcarbamoyl)thio)pentan-2-yl) 3-chlorobenzothioate,S-(4-((ethoxycarbonyl)oxy)pentan-2-yl) 3-chlorobenzothioate,S-(4-((ethoxycarbonyl)thio)pentan-2-yl) 3-chlorobenzothioate,4-((diethylcarbamoyl)thio)pentan-2-yl diethylcarbamate,4-((ethoxycarbonyl)thio)pentan-2-yl diethylcarbamate,4-((ethoxycarbonyl)thio)pentan-2-yl ethyl carbonate, O,O′-diethylS,S′-pentane-2,4-diyl dicarbonothioate, S,S′-pentane-2,4-diylbis(diethylcarbamothioate), S-(4-((ethoxycarbonyl)oxy)pentan-2-yl)diethylcarbamothioate, S-(4-((ethoxycarbonyl)thio)pentan-2-yl)diethylcarbamothioate, 4-((4-propylbenzoyl)thio)pentan-2-yl4-propylbenzoate, 4-((diethylcarbamoyl)thio)pentan-2-yl4-propylbenzoate, 4-((ethoxycarbonyl)thio)pentan-2-yl 4-propylbenzoate,S,S′-pentane-2,4-diyl bis(4-propylbenzothioate),S-(4-((diethylcarbamoyl)oxy)pentan-2-yl) 4-propylbenzothioate,S-(4-((diethylcarbamoyl)thio)pentan-2-yl) 4-propylbenzothioate,S-(4-((ethoxycarbonyl)oxy)pentan-2-yl) 4-propylbenzothioate,S-(4-((ethoxycarbonyl)thio)pentan-2-yl) 4-propylbenzothioate,4-((diethylcarbamoyl)thio)pentan-2-yl diethylcarbamate,4-((ethoxycarbonyl)thio)pentan-2-yl diethylcarbamate,4-((ethoxycarbonyl)thio)pentan-2-yl ethyl carbonate, O,O′-diethylS,S′-pentane-2,4-diyl dicarbonothioate, S,S′-pentane-2,4-diylbis(diethylcarbamothioate), S-(4-((ethoxycarbonyl)oxy)pentan-2-yl)diethylcarbamothioate, S-(4-((ethoxycarbonyl)thio)pentan-2-yl)diethylcarbamothioate, 2-((diethylcarbamoyl)thio)cyclohexyl benzoate,2-((ethoxycarbonyl)thio)cyclohexyl benzoate, 2-(benzoylthio)cyclohexylbenzoate, S,S′-cyclohexane-1,2-diyl dibenzothioate,S-(2-((diethylcarbamoyl)oxy)cyclohexyl) benzothioate,S-(2-((diethylcarbamoyl)thio)cyclohexyl) benzothioate,S-(2-((ethoxycarbonyl)oxy)cyclohexyl) benzothioate,S-(2-((ethoxycarbonyl)thio)cyclohexyl) benzothioate,2-((diethylcarbamoyl)thio)cyclohexyl diethylcarbamate,2-((ethoxycarbonyl)thio)cyclohexyl diethylcarbamate,2-((ethoxycarbonyl)thio)cyclohexyl ethyl carbonate,S,S′-cyclohexane-1,2-diyl O,O′-diethyl dicarbonothioate,S,S′-cyclohexane-1,2-diyl bis(diethylcarbamothioate),S-(2-((ethoxycarbonyl)oxy)cyclohexyl) diethylcarbamothioate,S-(2-((ethoxycarbonyl)thio)cyclohexyl) diethylcarbamothioate,2-((3-chlorobenzoyl)thio)cyclohexyl 3-chlorobenzoate,2-((diethylcarbamoyl)thio)cyclohexyl 3-chlorobenzoate,2-((ethoxycarbonyl)thio)cyclohexyl 3-chlorobenzoate,S,S′-cyclohexane-1,2-diyl bis(3-chlorobenzothioate),S-(2-((diethylcarbamoyl)oxy)cyclohexyl) 3-chlorobenzothioate,S-(2-((diethylcarbamoyl)thio)cyclohexyl) 3-chlorobenzothioate,S-(2-((ethoxycarbonyl)oxy)cyclohexyl) 3-chlorobenzothioate,S-(2-((ethoxycarbonyl)thio)cyclohexyl) 3-chlorobenzothioate,2-((diethylcarbamoyl)thio)cyclohexyl diethylcarbamate,2-((ethoxycarbonyl)thio)cyclohexyl diethylcarbamate,2-((ethoxycarbonyl)thio)cyclohexyl ethyl carbonate,S,S′-cyclohexane-1,2-diyl O,O′-diethyl dicarbonothioate,S,S′-cyclohexane-1,2-diyl bis(diethylcarbamothioate),S-(2-((ethoxycarbonyl)oxy)cyclohexyl) diethylcarbamothioate,S-(2-((ethoxycarbonyl)thio)cyclohexyl) diethylcarbamothioate,2-((4-propylbenzoyl)thio)cyclohexyl 4-propylbenzoate,2-((diethylcarbamoyl)thio)cyclohexyl 4-propylbenzoate,2-((ethoxycarbonyl)thio)cyclohexyl 4-propylbenzoate,S,S′-cyclohexane-1,2-diyl bis(4-propylbenzothioate),S-(2-((diethylcarbamoyl)oxy)cyclohexyl) 4-propylbenzothioate,S-(2-((diethylcarbamoyl)thio)cyclohexyl) 4-propylbenzothioate,S-(2-((ethoxycarbonyl)oxy)cyclohexyl) 4-propylbenzothioate,S-(2-((ethoxycarbonyl)thio)cyclohexyl) 4-propylbenzothioate,2-((diethylcarbamoyl)thio)cyclohexyl diethylcarbamate,2-((ethoxycarbonyl)thio)cyclohexyl diethylcarbamate,2-((ethoxycarbonyl)thio)cyclohexyl ethyl carbonate,S,S′-cyclohexane-1,2-diyl O,O′-diethyl dicarbonothioate,S,S′-cyclohexane-1,2-diyl bis(diethylcarbamothioate),S-(2-((ethoxycarbonyl)oxy)cyclohexyl) diethylcarbamothioate,S-(2-((ethoxycarbonyl)thio)cyclohexyl) diethylcarbamothioate,8-((diethylcarbamoyl)thio)naphthalen-1-yl benzoate,8-((ethoxycarbonyl)thio)naphthalen-1-yl benzoate,8-(benzoylthio)naphthalen-1-yl benzoate, S,S′-naphthalene-1,8-diyldibenzothioate, S-(8-((diethylcarbamoyl)oxy)naphthalen-1-yl)benzothioate, S-(8-((diethylcarbamoyl)thio)naphthalen-1-yl)benzothioate, S-(8-((ethoxycarbonyl)oxy)naphthalen-1-yl) benzothioate,S-(8-((ethoxycarbonyl)thio)naphthalen-1-yl) benzothioate,8-((diethylcarbamoyl)thio)naphthalen-1-yl diethylcarbamate,8-((ethoxycarbonyl)thio)naphthalen-1-yl diethylcarbamate,8-((ethoxycarbonyl)thio)naphthalen-1-yl ethyl carbonate, O,O′-diethylS,S′-naphthalene-1,8-diyl dicarbonothioate, S,S′-naphthalene-1,8-diylbis(diethylcarbamothioate), S-(8-((ethoxycarbonyl)oxy)naphthalen-1-yl)diethylcarbamothioate, S-(8-((ethoxycarbonyl)thio)naphthalen-1-yl)diethylcarbamothioate, 8-((3-chlorobenzoyl)thio)naphthalen-1-yl3-chlorobenzoate, 8-((diethylcarbamoyl)thio)naphthalen-1-yl3-chlorobenzoate, 8-((ethoxycarbonyl)thio)naphthalen-1-yl3-chlorobenzoate, S,S′-naphthalene-1,8-diyl bis(3-chlorobenzothioate),S-(8-((diethylcarbamoyl)oxy)naphthalen-1-yl) 3-chlorobenzothioate,S-(8-((diethylcarbamoyl)thio)naphthalen-1-yl) 3-chlorobenzothioate,S-(8-((ethoxycarbonyl)oxy)naphthalen-1-yl) 3-chlorobenzothioate,S-(8-((ethoxycarbonyl)thio)naphthalen-1-yl) 3-chlorobenzothioate,8-((diethylcarbamoyl)thio)naphthalen-1-yl diethylcarbamate,8-((ethoxycarbonyl)thio)naphthalen-1-yl diethylcarbamate,8-((ethoxycarbonyl)thio)naphthalen-1-yl ethyl carbonate, O,O′-diethylS,S′-naphthalene-1,8-diyl dicarbonothioate, S,S′-naphthalene-1,8-diylbis(diethylcarbamothioate), S-(8-((ethoxycarbonyl)oxy)naphthalen-1-yl)diethylcarbamothioate, S-(8-((ethoxycarbonyl)thio)naphthalen-1-yl)diethylcarbamothioate, 8-((4-propylbenzoyl)thio)naphthalen-1-yl4-propylbenzoate, 8-((diethylcarbamoyl)thio)naphthalen-1-yl4-propylbenzoate, 8-((ethoxycarbonyl)thio)naphthalen-1-yl4-propylbenzoate, S,S′-naphthalene-1,8-diyl bis(4-propylbenzothioate),S-(8-((diethylcarbamoyl)oxy)naphthalen-1-yl) 4-propylbenzothioate,S-(8-((diethylcarbamoyl)thio)naphthalen-1-yl) 4-propylbenzothioate,S-(8-((ethoxycarbonyl)oxy)naphthalen-1-yl) 4-propylbenzothioate,S-(8-((ethoxycarbonyl)thio)naphthalen-1-yl) 4-propylbenzothioate,8-((diethylcarbamoyl)thio)naphthalen-1-yl diethylcarbamate,8-((ethoxycarbonyl)thio)naphthalen-1-yl diethylcarbamate,8-((ethoxycarbonyl)thio)naphthalen-1-yl ethyl carbonate, O,O′-diethylS,S′-naphthalene-1,8-diyl dicarbonothioate, S,S′-naphthalene-1,8-diylbis(diethylcarbamothioate), S-(8-((ethoxycarbonyl)oxy)naphthalen-1-yl)diethylcarbamothioate, S-(8-((ethoxycarbonyl)thio)naphthalen-1-yl)diethylcarbamothioate,(9-(((diethylcarbamoyl)thio)methyl)-9H-fluoren-9-yl)methyl benzoate,(9-(((ethoxycarbonyl)thio)methyl)-9H-fluoren-9-yl)methyl benzoate,(9-((benzoylthio)methyl)-9H-fluoren-9-yl)methyl benzoate,S,S′-((9H-fluorene-9,9-diyl)bis(methylene)) dibenzothioate,S-((9-(((diethylcarbamoyl)oxy)methyl)-9H-fluoren-9-yl)methyl)benzothioate,S-((9-(((diethylcarbamoyl)thio)methyl)-9H-fluoren-9-yl)methyl)benzothioate,S-((9-(((ethoxycarbonyl)oxy)methyl)-9H-fluoren-9-yl)methyl)benzothioate,S-((9-(((ethoxycarbonyl)thio)methyl)-9H-fluoren-9-yl)methyl)benzothioate, (9-(((diethylcarbamoyl)thio)methyl)-9H-fluoren-9-yl)methyldiethylcarbamate,(9-(((ethoxycarbonyl)thio)methyl)-9H-fluoren-9-yl)methyldiethylcarbamate,(9-(((ethoxycarbonyl)thio)methyl)-9H-fluoren-9-yl)methyl ethylcarbonate, S,S′-((9H-fluorene-9,9-diyl)bis(methylene)) O,O′-diethyldicarbonothioate, S,S′-((9H-fluorene-9,9-diyl)bis(methylene))bis(diethylcarbamothioate),S-((9-(((ethoxycarbonyl)oxy)methyl)-9H-fluoren-9-yl)methyl)diethylcarbamothioate,S-((9-(((ethoxycarbonyl)thio)methyl)-9H-fluoren-9-yl)methyl)diethylcarbamothioate.

As explained above, the catalyst components comprise, in addition to theabove electron donors, Ti, Mg and halogen. In particular, the catalystcomponents comprise a titanium compound, having at least a Ti-halogenbond and the above mentioned electron donor compounds supported on a Mghalide. The magnesium halide may be MgCl₂ in active form, which is asupport for Ziegler-Natta catalysts. U.S. Pat. No. 4,298,718 and U.S.Pat. No. 4,495,338 were the first to describe the use of these compoundsin Ziegler-Natta catalysis. These patents describe magnesium dihalidesin active form used as support or co-support in components of catalystsfor the polymerization of olefins are characterized by X-ray spectra inwhich the most intense diffraction line that appears in the spectrum ofthe non-active halide is diminished in intensity and is replaced by ahalo whose maximum intensity is displaced towards lower angles relativeto that of the more intense line.

Titanium compounds for use in the catalyst component of the presentdisclosure are TiCl₄ and TiCl₃; furthermore, Ti-haloalcoholates offormula Ti(OR)_(m-y)X_(y) can be used, where m is the valence oftitanium, y is a number between 1 and m−1, X is halogen and R is ahydrocarbon radical having from 1 to 10 carbon atoms.

In a particular embodiment the amount of Ti atoms is higher than 2.5% wtincluding higher than 3.0% and in the range of 3.0 to 8% with respect tothe total weight of said catalyst component.

The preparation of the solid catalyst component can be carried outaccording to several methods. One method comprises the reaction betweenmagnesium alcoholates or chloroalcoholates (such as thechloroalcoholates prepared according to U.S. Pat. No. 4,220,554) and anexcess of TiCl₄ in the presence of the electron donor compounds at atemperature of about 80 to 120° C.

According to a method of the present technology, the solid catalystcomponent can be prepared by reacting a titanium compound of formulaTi(OR)_(m-y)X_(y), where m is the valence of titanium and y is a numberbetween 1 and m, such as TiCl₄, with a magnesium chloride deriving froman adduct of formula MgCl₂.pROH, where p is a number between 0.1 and 6,including from 2 to 3.5, and R is a hydrocarbon radical having 1-18carbon atoms. The adduct can be suitably prepared in spherical form bymixing alcohol and magnesium chloride in the presence of an inerthydrocarbon immiscible with the adduct, operating under stirringconditions at the melting temperature of the adduct (100-130° C.). Then,the emulsion is quickly quenched, thereby causing the solidification ofthe adduct in form of spherical particles. Examples of spherical adductsprepared according to this procedure are described in U.S. Pat. No.4,399,054 and U.S. Pat. No. 4,469,648. The so obtained adduct can bedirectly reacted with Ti compound or it can be previously subjected tothermal controlled dealcoholation (80-130° C.) so as to obtain an adductin which the number of moles of alcohol may be lower than 3, includingbetween 0.1 and 2.5. The reaction with the Ti compound can be carriedout by suspending the adduct (dealcoholated or as such) in cold TiCl₄(around 0° C.); the mixture is heated up to 80-130° C. and kept at thistemperature for 0.5-2 hours. The treatment with TiCl₄ can be carried outone or more times. The mercapto derivative electron donor compound maybe added during the treatment with TiCl₄. The preparation of catalystcomponents in spherical form are described in European PatentApplications EP-A-395083, EP-A-553805, EP-A-553806, EPA601525 andWO98/44001.

The solid catalyst components obtained according to the above methodshow a surface area (by B.E.T. method) between 20 and 500 m²/g andpreferably between 50 and 400 m²/g, and a total porosity (by B.E.T.method) higher than 0.2 cm³/g including between 0.2 and 0.6 cm³/g. Theporosity (Hg method) due to pores with radius up to 10.000 Å may rangefrom 0.3 to 1.5 cm³/g, including from 0.45 to 1 cm³/g. The solidcatalyst component has an average particle size ranging from 5 to 120 mincluding from 10 to 100 m.

In any of these preparation methods the desired electron donor compoundscan be added as such or, in an alternative way, it can be obtained insitu by using an appropriate precursor capable to be transformed in thedesired electron donor compound.

Regardless of the preparation method used, the final amount of theelectron donor compound of formula (I) is such that its molar ratio withrespect to the Ti atoms is from 0.01 to 2, including from 0.05 to 1.2.

The solid catalyst components according to the present technology areconverted into catalysts for the polymerization of olefins by reactingthe components with organoaluminum compounds.

An object of the present technology may involve a catalyst for thepolymerization of olefins CH₂═CHR, in which R is hydrogen or ahydrocarbyl radical with 1-12 carbon atoms, comprising the productobtained by contacting:

-   -   (i) the solid catalyst component as disclosed above and    -   (ii) an alkylaluminum compound and optionally,    -   (iii) an external electron donor compound

The alkyl-Al compound (ii) may be chosen from among the trialkylaluminum compounds such as for example triethylaluminum,triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum. It is also possible to use alkylaluminum halides,alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt₂Cland Al₂Et₃Cl₃, possibly in mixture with the above citedtrialkylaluminums.

External electron-donor compounds may include silicon compounds, ethers,esters, amines, heterocyclic compounds, including2,2,6,6-tetramethylpiperidine and ketones.

Another class of external donor compounds is that of silicon compoundsof formula (R₇)_(a)(R₈)_(b)Si(OR₉)_(c), where a and b are integers from0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R₇, R₈,and R₉, are radicals with 1-18 carbon atoms optionally containingheteroatoms. These compounds include silicon compounds in which a is 1,b is 1, c is 2, at least one of R₇ and R₈ is selected from branchedalkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionallycontaining heteroatoms and R₉ is a C₁-C₁₀ alkyl group, in particularmethyl. Examples of such silicon compounds aremethylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane,methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor),diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane,(2-ethylpiperidinyl)thexyldimethoxysilane,(3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane,methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane,N,N-diethylaminotriethoxysilane. Silicon compounds in which a is 0, c is3, R₈ is a branched alkyl or cycloalkyl group, optionally containingheteroatoms, and R₉ is methyl may also be used. Examples of such siliconcompounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane andthexyltrimethoxysilane.

The electron donor compound (iii) is used in such an amount to give amolar ratio between the organoaluminum compound and said electron donorcompound (iii) of from 0.1 to 500, preferably from 1 to 300 and from 3to 100.

Therefore, it constitutes a further embodiment of this disclosure aprocess for the (co)polymerization of olefins CH₂═CHR, in which R ishydrogen or a hydrocarbyl radical with 1-12 carbon atoms, carried out inthe presence of a catalyst comprising the product of the reactionbetween:

-   -   (i) the solid catalyst component comprising Mg, Ti and an        electron donor compound of formula (I) as above described;    -   (ii) an alkylaluminum compound and,    -   (iii) optionally an electron-donor compound (external donor).

The polymerization process can be carried out according to techniquessuch as slurry polymerization using as diluent an inert hydrocarbonsolvent, or bulk polymerization using the liquid monomer (for examplepropylene) as a reaction medium. Moreover, it is possible to carry outthe polymerization process in gas-phase operating in one or morefluidized or mechanically agitated bed reactors.

The polymerization may be carried out at temperature of from 20 to 120°C., including from 40 to 80° C. When the polymerization is carried outin gas-phase the operating pressure may be between 0.5 and 5 MPa,including between 1 and 4 MPa. In the bulk polymerization the operatingpressure may be between 1 and 8 MPa, including between 1.5 and 5 MPa.

The following examples are given in order to illustrate the disclosurewithout limiting it.

EXAMPLES

Characterizations

Determination of X.I.

2.5 g of polymer and 250 ml of o-xylene were placed in a round-bottomedflask provided with a cooler and a reflux condenser and kept undernitrogen. The obtained mixture was heated to 135° C. and was kept understirring for about 60 minutes. The final solution was allowed to cool to25° C. under continuous stirring, and the insoluble polymer was thenfiltered. The filtrate was then evaporated in a nitrogen flow at 140° C.to reach a constant weight. The content of said xylene-soluble fractionis expressed as a percentage of the original 2.5 grams and then, bydifference, the X.I. %.

Determination of Donors.

-   -   The content of electron donor has been carried out via        gas-chromatography. The solid component was dissolved in acidic        water. The solution was extracted with ethyl acetate, an        internal standard was added, and a sample of the organic phase        was analyzed in a gas chromatograph, to determine the amount of        donor present at the starting catalyst compound.

Melt Flow Rate (MFR)

-   -   The melt flow rate MIL of the polymer was determined according        to ISO 1133 (230° C., 2.16 Kg)

Ex 1. Synthesis of 2-(benzoylthio)-4-(tert-butyl)-3,6-dimethylphenylbenzoate First Step. Synthesis of4-(tert-butyl)-2-mercapto-3,6-dimethylphenol

The reaction is carried out in atmosphere of argon. The4-tert-butyl-2,5-dimethylphenol (20 g, 0.11 mol) is dissolved in 120 mLof toluene, containing 0.37 g of sulfur. The solution of 4.9 mL (0.062mol) of S₂Cl₂ in 50 mL of toluene is added slowly through the droppingfunnel with continued efficient stirring at such rate that the reactiontemperature does not exceed 30° C. When it is completed the solution isheated at 75° C. for 1 h and allowed to cool to room temperature Thereaction mixture is concentrated under low vacuum to have a residuevolume of about 60 mL. The suspension obtained is slowly added to asuspension of 5.38 g (0.14 mol) of LiAlH₄ in 180 mL of Et₂O.

The reaction mixture is refluxed for 6 h, stirred overnight and iscarefully treated with 5% HCl. Organic solution is separated, aqueouslayer is extracted with Et₂O several times. The combined organic phaseis dried over MgSO₄, evaporated and the residue is crystallized fromheptane. Yield 5.76 g (49%).

Second Step. Synthesis of2-(benzoylthio)-4-(tert-butyl)-3,6-dimethylphenyl benzoate

The solution of 4-(tert-butyl)-2-mercapto-3,6-dimethylphenol (10 g,0.048 mol) in toluene (290 mL) is treated sequentially with benzoylchloride (11.8 mL, 0.10 mol) and Et₃N (20.0 mL) at 0° C. After 16 h ofstirring at room temperature, it is poured into aqueous HCl and isdiluted with toluene (100 mL). The organic layer is washed sequentiallywith water, 2% aqueous NaOH, water, dried over MgSO₄, evaporated and theoil obtained is recrystallized from 95% EtOH (50 mL). Yield 15.5 g(78%).

Ex 2. Synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-6-methylphenyl ethyl carbonateFirst Step. Synthesis of 4-(tert-butyl)-2-mercapto-6-methylphenol

The reaction is carried out in atmosphere of argon. The4-tert-butyl-2-methylphenol (90 g, 0.5 mol) is dissolved in 250 mL oftoluene, containing 0.5 g of sulfur. The solution of 22 mL (0.55 mol) ofS₂Cl₂ in 100 mL of toluene is added slowly through the dropping funnelwith continued efficient stirring at such rate that the reactiontemperature does not exceed 30° C. Then the solution is heated at 75° C.for 1 h and allowed to cool to room temperature. The toluene is removedunder low vacuum and the residue is dissolved in 200 mL of Et₂O. Thesolution obtained is slowly added to a suspension of 24 g (0.63 mol) ofLiAlH₄ in 600 mL of Et₂O.

The reaction mixture is refluxed for 6 h, stirred overnight andcarefully treated with 5% HCl. Organic layer is separated and aqueouslayer is extracted with Et₂O several times. The combined organic phaseis dried over MgSO₄, evaporated and distilled. Yield 50.1 g (47%).

Second Step. Synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-6-methylphenyl ethyl carbonate

The solution of 4-(tert-butyl)-2-mercapto-6-methylphenol (7.88 g, 0.0342mol) in toluene (150 mL) is treated sequentially with pyridine (12 mL)and ethyl chloroformate (7.19 mL, 0.0752 mol) with stirring and cooling(0° C.). After stirring at room temperature for 16 h the reactionmixture is treated with water and is diluted with toluene (100 mL). Theorganic layer is washed sequentially with aqueous HCl and water, driedover MgSO₄, evaporated and distilled in vacuum (165° C./0.5 mmHg). Yield8.9 g (73%).

Ex 3. Synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3,6-dimethylphenyl ethylcarbonate

The procedure is the same as that used in the Ex 2 except that4-(tert-butyl)-2-mercapto-3,6-dimethylphenol is used instead of4-(tert-butyl)-2-mercapto-6-methylphenol. After distillation yield of73%.

Ex 4. One-pot synthesis of4-(tert-butyl)-2-((diethylcarbamoyl)thio)-6-methylphenyl3-chlorobenzoate

The solution of 4-(tert-butyl)-2-mercapto-6-methylphenol (9.82 g, 0.05mol) in pyridine (40 mL) is treated in 30 min with diethylcarbamoylchloride (7.0 g, 0.05 mol) at stirring and cooling (−30° C.). Afterstirring at room temperature for 16 h, the reaction mixture is treatedwith 3-chlorobenzoyl chloride (9.1 g, 0.05 mol) also with stirring andcooling (0° C.). After stirring at room temperature for additional 16 h,the reaction mixture is poured into the water-ice mixture containing 80mL of conc. HCl. Then it is extracted with CH₂Cl₂ and the organic phaseis washed sequentially with aqueous HCl, water, 5% solution of NaOH,water and dried over MgSO₄ and concentrated. The product is purified bycolumn chromatography on neutral Al₂O₃ with using of toluene/hexanemixture (1/2) as eluent. Yield 10.0 g (46%).

Ex 5. One-pot synthesis of4-(tert-butyl)-2-((dimethylcarbamoyl)thio)-6-methylphenyl3-chlorobenzoate

The procedure is the same as that used in the Ex 4 except thatdimethylcarbamoyl chloride is used instead of diethylcarbamoyl chloride.Yield 72%.

Ex 6. One-pot synthesis ofS-(5-(tert-butyl)-2-((ethoxycarbonyl)oxy)-3-methylphenyl)dimethylcarbamothioate

The procedure is the same as that used in the Ex 4 except that ethylchloroformate is used instead of 3-chlorobenzoyl chloride. Yield 59%.

Ex 7. One-pot synthesis ofS-(5-(tert-butyl)-2-((ethoxycarbonyl)oxy)-3-methylphenyl)diethylcarbamothioate

The procedure is the same as that used in the Ex 6 except thatdiethylcarbamoyl chloride is used instead of dimethylcarbamoyl chloride.Yield 57%.

Ex 8. One-pot synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3,6-dimethylphenyl3-chlorobenzoate

The solution of 4-(tert-butyl)-2-mercapto-6-methylphenol (9.0 g, 0.043mol) and pyridine (16 mL) in toluene (160 mL) is treated in 3 h with asolution of ethyl chloroformate (4.64 g, 0.043 mol) in toluene (30 mL)at stirring and cooling (0° C.). After stirring at room temperature for16 h, the reaction mixture is treated with 3-chlorobenzoyl chloride(7.53 g, 0.043 mol) also at stirring and cooling (0° C.). After 16 h ofstirring at room temperature, it is poured at the shaking into aqueousHCl and is diluted by toluene (100 mL). The organic layer is washedsequentially with water, 2% aqueous NaOH, water, dried over MgSO₄,evaporated and the oil obtained is recrystallized from petroleum ether.Yield 11.6 g (64%).

Ex 9. One-pot synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3,6-dimethylphenyl benzoate

The procedure is the same as that used in the Ex 8 except that benzoylchloride is used instead of 3-chlorobenzoyl chloride. Yield aftercrystallization from heptane is 54%.

Ex 10. One-pot synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3,6-dimethylphenyl4-methylbenzoate

The procedure is the same as that used in the Ex 8 except that4-methylbenzoyl chloride is used instead of 3-chlorobenzoyl chloride.Yield after crystallization from petroleum ether is 56%.

Ex 11. One-pot synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-6-methylphenyl 3-chlorobenzoate

The procedure is the same as that used in the Ex 8 except that4-(tert-butyl)-2-mercapto-6-methylphenol is used instead of4-(tert-butyl)-2-mercapto-3,6-dimethylphenol. Yield aftercrystallization from petroleum ether is 46%.

Ex 12. One-pot synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-6-methylphenyl benzoate

The procedure is the same as that used in the Ex 9 except that4-(tert-butyl)-2-mercapto-6-methylphenol is used instead of4-(tert-butyl)-2-mercapto-3,6-dimethylphenol. Yield aftercrystallization from mixture of petroleum ether/CHCl₃ (about 1/1) is34%.

Ex 13. One-pot synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-6-methylphenyl 4-methylbenzoate

The procedure is the same as that used in the Ex 10 except that4-(tert-butyl)-2-mercapto-6-methylphenol is used instead of4-(tert-butyl)-2-mercapto-3,6-dimethylphenol. Yield aftercrystallization from petroleum ether is 38%.

Ex 14. One-pot synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-3,6-dimethylphenylfuran-2-carboxylate

The procedure is the same as that used in the Ex 11 except that 2-furoylchloride is used instead of 3-chlorobenzoyl chloride. Yield aftercrystallization from petroleum ether and EtOH is 56%.

Ex 15. One-pot synthesis of4-(tert-butyl)-2-((ethoxycarbonyl)thio)-6-methylphenyl diethylcarbamate

A solution of 4-(tert-butyl)-2-mercapto-6-methylphenol (18.83 g, 0.096mol) and pyridine (27 mL) in toluene (350 mL) was treated in 4 h with asolution of ethyl chloroformate (9.15 mL, 0.097 mol) in toluene (50 mL)under stirring and cooling (0° C.). After stirring at room temperaturefor 16 h, the mixture was treated with diethylcarbamoyl chloride (20 mL,0.158 mol) and Et₃N (20 mL) also under stirring and cooling (0° C.).After 48 h of stirring at room temperature, it was quenched with aqueousHCl and was diluted with toluene (100 mL). The organic layer was washedwith water, dried over MgSO₄, evaporated and the residue obtained wasdistilled in vacuum (180-182° C./0.3 mmHg). Yield 8.4 g (24%).

Ex 16. Synthesis ofS-(5-cyclohexyl-2-((ethoxycarbonyl)oxy)-3-methylphenyl)dimethylcarbamothioate First Step: Synthesis of4-cyclohexyl-2-mercapto-6-methylphenol

A solution of S₂Cl₂ (20 mL, 0.25 mol) in toluene (250 mL) was treatedwith a solution of 4-cyclohexyl-2-methylphenol (47.6 g, 0.25 mol) intoluene (250 mL) under stirring. After addition the solution was stirredfor additional 2 h. The solvent was evaporated under vacuum, the residuewas dissolved in 95% EtOH (400 mL), then zinc powder was added (50 g,0.79 mol) followed by concentrated HCl added dropwise (190 mL) at 0° C.and stirring. After addition the mixture was stirred for additional 2 h.The reaction mixture was poured into water (900 mL) and was extractedwith CH₂Cl₂ several times. The combined organic phase was dried overMgSO₄, evaporated and the residue was distilled under vacuum (133-136°C./0.5 mmHg). Yield 26.7 g (48%).

Second Step. Synthesis ofS-(5-cyclohexyl-2-((ethoxycarbonyl)oxy)-3-methylphenyl)dimethylcarbamothioate

A solution of 4-cyclohexyl-2-mercapto-6-methylphenol (16.68, 0.075 mol)and pyridine (19 mL) in toluene (180 mL) was treated in 30 min withdimethylcarbamoyl chloride (8.47 g, 0.082 mol) under stirring andcooling (0° C.). After stirring at room temperature for 16 h, thereaction mixture was treated with ethyl chloroformate (9.77 mL, 0.09mol) also under stirring and cooling (0° C.). After stirring at roomtemperature for additional 16 h, the reaction mixture was poured into awater-ice mixture containing 30 mL of conc. HCl. Then it was extractedwith CH₂Cl₂, the organic phase was washed sequentially with aqueous HCland water, dried over MgSO₄, evaporated and the residue was distilledunder vacuum (212-215° C./0.4 mmHg). Yield 11.4 g (42%).

Ex 17. Synthesis of syn S,S′-pentane-2,4-diyl dibenzothioate First Step:Synthesis of syn-pentane-2,4-diyl bis(4-methylbenzenesulfonate)

A 250 mL reaction vessel is charged with syn 2,4-pentanediol (10 g, 95.1mmol) and pyridine (70 g). The mixture is cooled to −10° C. andp-toluenesulfonyl chloride (40.3 g, 2.2 eq) is slowly added. The mixtureis allowed to stir at ambient temperature for 15 h. Ethyl acetate (100mL) is added to the reaction mixture and the resulting organic layer iswashed with a saturated aqueous NH₄Cl solution and a saturated aqueousNaCl solution, then dried over MgSO₄, filtered and concentrated on arotary evaporator which resulted in the crude product as a hell yellowsolid.

Second Step: Synthesis of syn S,S′-pentane-2,4-diyl dibenzothioate

A 100 mL reaction vessel is charged with syn pentane-2,4-diylbis(4-methylbenzenesulfonate) (5.6 g, 13.4 mmol), benzenecarbothioicS-acid (4.13 g, 2 eq), NaHCO₃ (2.28 g, 2 eq) and DMF (25 mL). Themixture is allowed to stir at 80° C. for 2 h. The red solution isdiluted with ethyl acetate (50 mL) and the resulting solution is washedwith a saturated aqueous NaHCO₃ solution and a saturated aqueous NaClsolution. The organic layer is dried over MgSO₄, filtered andconcentrated on a rotary evaporator which resulted in the crude productas a red oil. It is purified by means of chromatography(SiO₂)-cyclohexane/ethyl acetate: 40/1. Yield: 2 g (43.3%).

Ex 18. Synthesis of S,S′-pentane-2,4-diyl bis(4-propylbenzothioate)First Step: Synthesis of S,S′-pentane-2,4-diyl diethanethioate

A 250 mL reaction vessel is charged with pentane-2,4-diylbis(4-methylbenzenesulfonate) (19 g, 45.6 mmol) potassium thioacetate(15.78 g, 3 eq) and DMF (70 mL). The mixture is allowed to stir atambient temperature for 12 h. The red solution is diluted with ethylacetate (200 mL) and the resulting solution is washed with a saturatedaqueous NaHCO₃ solution and a saturated aqueous NaCl solution. Theorganic phase is dried over MgSO₄, filtered and concentrated on a rotaryevaporator which resulted in the crude product as a red oil. It ispurified by means of distillation. Yield: 8.1 g (80%)—yellow oil.

Second Step: Synthesis of S,S′-pentane-2,4-diylbis(4-propylbenzothioate)

A 100 mL reaction vessel is charged with S,S′-pentane-2,4-diyldiethanethioate (5 g, 22.5 mmol) and methanol (50 mL). Sodium methoxide(2.57 g, 2.1 eq) is then slowly added at ambient temperature. Themixture is allowed to stir for 2 h. Methanol is removed by distillationand the resulting orange oil is diluted with pyridine (50 mL). It iscooled to 0° C. and 4-n-propyl-benzoyl chloride (11.08 g, 2.7 eq) isslowly added and stirred for 12 h. Pyridine is removed by distillationand the resulting oil is diluted with ethyl acetate (100 mL). Theresulting solution is washed with a saturated aqueous NaHCO₃ solutionand a saturated aqueous NaCl solution. The organic phase is dried overMgSO₄, filtered and concentrated on a rotary evaporator which resultedin the crude product as a yellow oil. It is purified by means ofchromatography (SiO₂)-cyclohexane/ethyl acetate: 60/1. Yield: 4.4 g(45.6%).

Procedure for the Preparation of the Solid Catalyst Component UsingDonors Ex 1-17.

Into a 500 mL round bottom flask, equipped with mechanical stirrer,cooler and thermometer 250 mL of TiCl₄ were introduced at roomtemperature under nitrogen atmosphere. After cooling to 0° C., whilestirring, the internal donor and 10.0 g of the spherical adduct(prepared as described above) were sequentially added into the flask.The amount of charged internal donor was such to charge a Mg/donor molarratio of 6. The temperature was raised to 100° C. and maintained for 2hours. Thereafter, stirring was stopped, the solid product was allowedto settle and the supernatant liquid was siphoned off at 100° C. Afterthe supernatant was removed, additional fresh TiCl₄ was added to reachthe initial liquid volume again. The mixture was then heated at 120° C.and kept at this temperature for 1 hour. Stirring was stopped again, thesolid was allowed to settle and the supernatant liquid was siphoned off.

The solid was washed with anhydrous hexane six times (6×100 mL) intemperature gradient down to 60° C. and one time (100 mL) at roomtemperature. The obtained solid was then dried under vacuum andanalyzed.

Procedure for the Preparation of the Solid Catalyst Component UsingDonor Ex 18.

Into a 500 mL round bottom flask, equipped with mechanical stirrer,cooler and thermometer 250 mL of TiCl₄ were introduced at roomtemperature under nitrogen atmosphere. After cooling to 0° C., whilestirring, ethyl benzoate and 10.0 g of the spherical adduct (prepared asdescribed above) were sequentially added into the flask. The amount ofcharged ethyl benzoate was such to charge a Mg/EB molar ratio of 4. Thetemperature was raised to 100° C. and maintained for 2 hours.Thereafter, stirring was stopped, the solid product was allowed tosettle and the supernatant liquid was siphoned off at 100° C. After thesupernatant was removed, additional fresh TiCl₄ was added to reach theinitial liquid volume again followed by the addition of the internaldonor with Mg/donor ratio of 6. The mixture was then heated at 120° C.and kept at this temperature for 1 hour. Stirring was stopped again, thesolid was allowed to settle and the supernatant liquid was siphoned off.This last hot treatment at 120° C. for 1 hour is repeated an additionaltime. Stirring was stopped again, the solid was allowed to settle andthe supernatant liquid was siphoned off.

The solid was washed with anhydrous hexane six times (6×100 mL) intemperature gradient down to 60° C. and one time (100 mL) at roomtemperature. The obtained solid was then dried under vacuum andanalyzed.

General Procedure for the Polymerization of Propylene

A 4-liter steel autoclave equipped with a stirrer, pressure gauge,thermometer, catalyst feeding system, monomer feeding lines andthermostating jacket, was purged with nitrogen flow at 70° C. for onehour. Then, at 30° C. under propylene flow, were charged in sequencewith 75 ml of anhydrous hexane, 0.76 g of AlEt₃, 0.076 g ofdicyclopentyldimethoxysilane (D donor) and 0.006÷0.010 g of solidcatalyst component. The autoclave was closed; subsequently 2.0 Nl ofhydrogen were added. Then, under stirring, 1.2 kg of liquid propylenewas fed. The temperature was raised to 70° C. in five minutes and thepolymerization was carried out at this temperature for two hours. At theend of the polymerization, the non-reacted propylene was removed; thepolymer was recovered and dried at 70° C. under vacuum for three hours.Then the polymer was weighed and fractionated with o-xylene to determinethe amount of the xylene insoluble (X.I.) fraction.

TABLE 1 Composition and performance of exemplified catalysts Catalystcompostion Polymerization Internal Donor Ti Mileage XI MIL Ex.Structure/Name % wt % wt ED kg/g % wt g/10′  1

11.6 4.3 D 62 98.6 1.8  2

18.3 3.4 D 37 97.5 2.9  3

18.1 3.5 D No ED 41 80 98.2 94.3 3.6 4.7  4

n.d. 4.5 D 80 97.3 n.d.  5

15.0 4.0 D 81 96.4 2.1  6

15.9 4.2 D 71 97.8 2.3  7

12 4.8 D 67 97.4 n.d.  8

n.d. 3.6 D 42 98.6 n.d.  9

14.7 4.0 D 70 98.9 2.2 10

n.d. 4.1 D 88 98.6 1.0 11

14.3 3.8 D 57 98.8 1.9 12

16.4 4.4 D 66 98.1 2.6 13

10.6 3.5 D 76 98.3 1.5 14

n.d. 3.7 D 55 97.8 3.0 15

n.d. 5.0 D 71 97.2 5.7 16

10.7 4.3 D 63 97.6 2.7 17

n.d. 3.7 D 28 97.4 2.1 18

n.d. 4.0 D 73 97.1 1.7 ED: External Donor. D:dicyclopentyldimethoxysilane

What is claimed is:
 1. A solid catalyst component for the polymerizationof olefins comprising Mg, Ti, Cl and at least an electron donor compoundof formula (II)

in which B is oxygen or sulphur S is sulfur, R⁴-R⁷ groups, equal to ordifferent from each other, are hydrogen or C₁-C₁₅ hydrocarbon groups,optionally containing an heteroatom selected from halogen, P, S, N andSi, and R⁸, equal to or different from each other, are selected fromC₁-C₁₅ hydrocarbon groups which can be optionally linked to form a cycleand n is an integer from 0 to
 5. 2. The solid catalyst component ofclaim 1 in which B is sulfur and R⁴ and R⁷ are selected from C₁-C₁₀alkyl groups.
 3. The solid catalyst component of claim 2 in which R⁴ andR⁷ are selected from from C₁-C₅ alkyl groups and R⁵ and R⁶ are selectedfrom hydrogen or C₁-C₁₀ alkyl groups.
 4. The solid catalyst component ofclaim 1 in which R⁸ groups are independently selected from C₁-C₁₀ alkylgroups.
 5. The solid catalyst component of claim 4 in which R⁸ groupsare independently selected from C₁-C₅ alkyl groups.
 6. The solidcatalyst component of claim 5 in which R⁸ groups are independentlyselected from the group consisting of methyl, ethyl, n-propyl andn-butyl.
 7. The solid catalyst component of claim 1 in which the index nranges from 1 to
 3. 8. The solid catalyst component of claim 7 in whichthe index n is
 1. 9. The solid catalyst component of claim 1 in whichthe substituent R⁸ is in position 4 of the benzoate ring.
 10. A catalystfor the polymerization of olefins comprising the product of the reactionbetween: the solid catalyst component of claim 1, an alkylaluminumcompound and optionally, an external electron donor compound.
 11. Aprocess for the (co)polymerization of olefins CH₂═CHR′, in which R′ ishydrogen or a hydrocarbyl radical with 1-12 carbon atoms, wherein thecatalyst of claim 10 is contacted with the olefins in the gas phase inone or more fluidized or mechanically agitated bed reactors.